Method for fire-proofing treatment of fabrics composed of polyester and cellulosic filaments or fibers

ABSTRACT

A method for fire-proofing treatment of a fabric composed of polyester and cellulosic filaments of fibers, which comprises impregnating said fabric with the following treating agents: (1) a tetrakis-hydroxymethyl phosphonium compound, (2) methylolmelamine, (3) a specific thiocarbamic acid derivative, (4) a specific organic halogenated phosphorus compound and (5) a specific long-chain alkylethyleneurea, the amounts of the treating agents (1), (2), (3), (4) and (5), when designated a, b, c, d and e respectively, being as follows based on the total weight of a to e, A 40 TO 80 PERCENT, B 10 TO 50 PERCENT, C 5 TO 25 PERCENT, D 3 TO 10 PERCENT, E 1 TO 5 PERCENT AND SATISFYING THE FOLLOWING EQUATION   AND HEAT-SETTING THE IMPREGNATED FABRIC.

" a 55R its .5 Q it g; a, A 5/ 231:? J I! 22!??? L X mic I, A i "I If v I s v 'V I; United States g/$9 W l 1 3,930,079 Hashizume et als1 Dec. 30, 1975 [54] METHOD FOR FIRE'PROOFING Primary ExamineP-Ralph S. Kendall TREATMENT OF FABRICS COMPOSED OF Attorney, Agent, or FirmSherman & Shalloway POLYESTER AND CELLULOSIC FILAMENTS OR FIBERS [57] ABSTRACT [75] Inventors: Astuo l if Kyoto; f l A method for fire-proofing treatment of a fabric com- Tsuzukl l Harm) Mlzushlm posed of polyester and cellulosic filaments of fibers, Takatsukl of Japan which comprises impregnating said fabric with the fol- [73] Assignee: Teijin Limited, Osaka, Japan lowing treating agents: (1) a tetrakis-hydroxymethyl phosphonium compound, (2) methylolmelamine, (3)

[22] Flled' i 1974 a specific thiocarbamic acid derivative, (4) a specific [21] Appl. No.: 532,239 organic halogenated phosphorus compound and (5) a specific long-chain alkylethyleneurea, the amounts of the treating agents (1), (2), (3), (4) and (5), when Forelg Apphcatlon Pnonty Data designated a, b, c, d and e respectively, being as fol- Dec. 12, 1973 Japan 48-137679 lows based on the total weight of a to e,

a to 80 percent, [52] US. Cl. 427/396; 8/116 P, 8/195; 1; 10 to 50 percent,

106/15 428/277 0 5 to 25 percent, [51] Int. Cl. DOGM 13/28; CO9K 3/28 d 3 to l() percent, [58] Field of Search 428/276, 277, 921, 920; e 1 t 5 er ent 106/15 PP; 8/116 191; and satisfying the following equation [56] References Cited UNITED STATES PATENTS 4 m 3,247,015 4/1966 Zimmerman et a]. 428/277 3,376,l 4/1968 Le Blanc 3,759,851 9/1973 Carl et al. 428/277 OTHER PUBLICATIONS and heat-setting the impregnated fabric.

A Study of Fire Retardancy of Polyester/Cotton 6 Claims, No Drawings Sheeting, American Dyestuff Reporter, May 6, 1968, pp. 373-377.

METHOD FOR FIRE-PROOFING TREATMENT OF FABRICS COMPOSED F POLYESTER AND CELLULOSI'C FILAMENTS 0R FIBERS This invention relates to :a method for fire-proofing treatment of fabrics composed of polyester and cellulosic filaments or fibers to impart-to the fabrics not only a high level of fire-proofness but" also otherimproved properties such as moderate stiffness, resistance to dye bleed-out, rust-proofness, resistance to soiling and superior feel (free from a tacky feeling):

More specifically, this invention relates to a method for fire proofing treatment of fabrics composed of polyester and cellulosic filaments or fibers, which comprises impregnating the fabrics with the following treating agents (l) to l. a tetrakis-hydroxymethyl phosphonium compound,

2. methylolmelamine,

3. a thiocarbomaic acid derivative of the formula wherein X is a group selected from the class consisting of wherein R R and R are the same of different, and each represent a monovalent hydrocarbon group containing 1 to l 2 carbon atoms, at least 'one of R R and R contains atleast one halogen atom selected from the group consisting of brominezand chlorine, R R and R], are the same or different and each represent a monovalent' hydrocarbon group containing 1 to 12 carbon atoms, and'at le'ast one of R R and R contains at least one halogen atom selected from the group consisting of bromine and chlorine, and I 5. a long-chain alkyl ethyleneurea of the formula velop rust. Moreover, the fabric assumes a tacky feelwherein R is 'aim onovalent saturated alkyl group containi ng 8 to22 carbon atoms, the amountsiof the treating agents l (2), (3), (4) and (5 )","when designateda, b, c, a and' e respectively, being as follows based on the total weight of ('1 to e 40 to '80 percent b=l0 to' 5O percent (=5 to 25 percent d="3 r010 percent e=l to 5 percent t and satisfying the following equation and heat-setting the impregnated fabrics.

'' 'It has previously been known to impart fireproofness to afabric composed of polyester and cellulosic filaments or fibers by treating the fabric with an aqueous dispersion of tetrakis-hydroxymethyl phosphonium compound [THPCfor short; the treating agent (1) above], trimethylolmelamine {corresponding to the treating agent (2) above], ureas [not included within the treating agent (3) above], and tris (2,3-dibromopropylyphosphate ,[DBP-P for short; corresponding to the'treating agent(4) above] (American Dyestuff Reporter, Vol. 57, page 373,,1968);

This methodseems feasible insofar as a THPC type fire-proofing agent for cellulosic fibers and a halogenated phosphate. type fire-proofing agent (DBPP) for polyesters are used .in combination. in this method, DBPP is used in an amount .of as much as about 38 percent by weight based on the total amount of THPC, trimethylolrnelamine and urea, butdespite such a large amount of DBPP, the fire-proofness imparted is insufficient, and does not meet the acceptance criterion, for example, of a fire-proofness test by a vertical testing method (standard for the Flammability of Childrens Sleepear DO'C FF 3-71). Moreover, when DBPP is used in such an amount, undesirable effects are exerted on 'the color of a dyed fabric, or the dye bleeds out, or the sunlight fastness of the d'yeingis reduced. Furthermore, when such'a fabric is used' in curtains, curtain rails or metal fixtures'in contact with the curtain deing or waxy feeling which degrades the commercial value of the fabric, or becomes liable to be soiled.

If in an attempt to avoid these defects, the amount of DBPP is r'educed, for example to one-fourth to one tenth of the amount used in the above-cited method, the fire-proofness will be reduced drastically, and in an extreme case; therewill be no significance of the treatment. In additionfthe fabricstreated become harsh in feeling and lose their practical value.

We have now found unexpectedly that fabrics composedof polyester and cellulosic filaments or fibers can be rendered fire-proof by treatment with l) a tetrakishydroxymethyl phosphonium compound, (2) methylolmelamine, (3) a thiocarbamic acid derivative, (4) an organic halogenated phosphorus compound and (5) a long-chain alkyl ethyleneurea in the specific amounts hereinafter described without involving any of the above-mentioned defects of the prior techniques.

Accordingly, it is an object of this invention to provide a method for fire-proofing treatment of a fabric composed of polyester and cellulosic filaments or fibers by which not only a high level of fire-proofness but also other improved properties such as moderate stiffness, resistance to dye bleed-out, rust-proofness, resistance to soiling and superior feel can be imparted to the treated fabric.

Other objects of this invention together with its advantages will become apparent from the following descriptions.

The fabric composed of polyester and cellulosic filaments or fibers, as termed in this application, is meant to refer generically to fibrous structures composed of these two types of material which may be in any desired form such as a monofilament, multifilament, staple fiber, yarn, or tow. The fabric may be in any desired form such as a knitted, woven or non-woven fabric.

Preferably, the fabric to be rendered fireproof by the method of this invention consists, based on the weight of the fabric, of about 50 to about 70 percent of polyestcr filaments or fibers and about 50 to about 30 percent of cellulosic filaments or fibers. Polyester-cellulosic mixed type fabrics within this mixing ratiohave previously been especially difficult to render fire-proof to a satisfactory degree. According to this invention, an outstanding fireproofing effect can be imparted even to such fabrics along with the above-mentioned improved properties.

The polyester as a raw material for the polyester filaments or fibers may, for example, be polyethylene terephthalate, polyethylene-Z,6-naphthalate, or polyesters composed mainly of polyethylene terephthalate and a third component incorporated for dyeability improvement. Examples of the cellulosic filaments or fibers are filaments or fibers of cellulosic materials such as cotton, flax, other natural celluloses, viscose rayon, or cellulose acetate rayon. Fabrics composed of these polyester and cellulosic materials can contain up to about percent by weight, based on the total weight of these materials, of another natural or synthetic fiberforming material.

Examples of the tetrakis-hydroxymethyl phosphonium compound (THPC) 1) used in this invention are tetrakishydroxymethyl phosphonium halides, preferably the chloride, and tetrakishydroxymethyl phosphonium hydroxide. The hydroxide can be obtained by treatiing a salt of tetrakis-hydroxymethyl phosphonium in an aqueous solution ofa base such as sodium hydroxide.

The methylolmelamine (2) used in this invention includes mono-, di-, tri-, tetra-, pentaand hexamethylolmelamines, and may also be their etherified products such as etherified methylolmelamines etherified partially with propanol or butanol, or pre-condensation products of methylolmelamine. Usually, the precondensation products not precipitable in cold water can be preferably utilized.

Preferred thiocarbamic acid derivatives as treating agent (3) used in this invention are those in which X is -NH and which is expressed by the following formula 4 wherein each of R' and R g is hydrogen atom or a hydrocarbon group containing 1 to 6 carbon atoms, and R or R may, together with an amino group, form a nitrogen-containing cyclic structure having a lower alkylene linkage. Specific examples of these thiocabamic acid derivatives are thiourea, ethylene thiourea, diphenyl thiourea, thiobiuret, ethyl thiocarbamate, cyclohexyl thiocarbamate, and propylene thiourea. Preferred organic halogenated phosphorus compounds used as agent (4) in this invention are those expressed by the following formulas wherein R R and R',, are the same or different and each represent a monovalent hydrocarbon group containing 1 to 6 carbon atoms, preferably an alkyl group containing 1 to 6 carbon atoms or a phenyl group that may be substantituted by a lower alkyl group containing 1 to 4 carbon atoms, at least one of R',,, R and R',, contains at least one halogen atom selected from the group consisting of bromine and chlorine, R' R' and R' are the same or different, and each represent a monovalent hydrocarbon group containing 1 to 6 carbon atoms, preferably an alkyl group containing 1 to 6 carbon atoms or a phenyl group that may be substituted with a lower alkyl group containing 1 to 4 carbon atoms, and at least one of R' R and R',, contains at least one halogen atom selected from the group consisting of bromine and chlorine.

Specific examples of compounds of (R 0) (R 0) (R O)P=O are tris (2,3-dibromopropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris(bromochloropropyl) phosphate, tris (bromochloropropyl) phosphate, tris (monobromopropyl) phosphate, tris(monochloropropyl) phosphate, tris(2-chloroethyl) phosphate, polybrominated triphenyl phosphate, dimethylmono- (dibromocresyl) phosphate, and polybrominated triphenyl phosphate. The tris(2,3-dibromopropyl) phosphate and tris(bromochloropropyl) phosphate are especially preferred.

Specific examples of the compounds of the formula (R9)(R 0O)(R O)P=O are bis(bromochloropropyl) bromochloropropyl phosphonate, bis(pentabromocresyl) pentabromocresyl phosphonate, and bis(dibromopropyl) dibromopropyl phosphonate. The bis(dibromopropyl) dibromopropyl phosphonate is especially preferred.

Preferred long-chain alkyl ethyleneureas as treating agent (5) used in this invention are those expressed by the following formula 5 wherein R',: is a monovalentsaturated alkyl group containing l6 to 20 carbon atoms. Specific examples of these long-chain alkyl ethylencureas are decyl ethyleneurea, tetradecyl cthylc-neurea, hexadecyl ethyleneurea, octadecyl ethyleneurea, and eicosyl ethyleneurea.

In each of the treating agents l to (5 two or more kinds canof course be used.

In the method of this invention, fabrics composed of polyester and cellulosic filaments of fibers are treated with the treating agents l to (5 Any means by which to impregnate the fabric with these treating agents can be used in the method of'this invention. Usually, the fabric is dipped in a bath containing these treating agents, or the fabric is caused to pass'through this bath. If desired, other means of impregnation, such as roll coating or spray coating, can also be used.

The treating agents can be used in the form of an aqueous dispersion or a solution in an organic solvent such as methanol, ethanol, benzene, toluene or xylene. Alternatively, the organic halogenated phosphorus compound is applied to the fabric in the form of an organic solvent solution in the first step, and then in the second step, the other four treating agents are applied to the fabric in the form of an aqueous solution. The treating bath may contain an alkali such as sodium hydroxide (acting to convert a salt of tetrakis-hydroxymethyl phosphonium to its hydroxide) or a nonionic, anionic or cationic surface active agent or an antistatic agent. The amount of the surface active agent or the antistatic agent must be not in excess of 10% based on the total amount of'the above five treating agents. Too

compared with that of the treating agents (1), (2) and (3) (u% b71- various defects of the conventional techniques, such as bleed-out of dye, change in color, reduction in sunlight fastness, rust formation in metals incontact with the fireproofed fabric, the tacky feeling or waxy feeling of the treated fabric, or its sus ceptibility to soiling, can be removed.

It has not yet been clear why the conjoint use of the treating agents (1) to can provide the above-mentioned improved properties which have previously been unable to stand together in the fire-proofed polyestercellulose fabrics. While in the conventional process, THPC as treating agent (I) acts independently on the burning behavior of cellulosic materials and the organic halogenated phosphorus compound as treating agent (4), on the burning behavior of polyester materials, the combination of the treating agents (3), (4) and (5) in the present invention provides a synergistic effect of fire-proofing elements, P+N+S+X (halogen), not seen'in the conventional treating methods, and these elements simultaneously act with good efficiency during the burning of the polyester-cellulose fabrics. This is presumed to be the reason for the superior fireproofing effect obtained by the present invention. On the other hand, the moderate stiffness of the treated fabric is presumably because the treating agent (5) interacts with the treating agents (1), (2), (3) and (4) during the step of heat-setting the fabric to cause a change in the behavior of fixation of the treating agents in the fibers or on the surface of the fibers, and the heat-setting is effectedwhile the degree of intertwining great an amount of such an additive is undesirable because it results in reduced fire-proofness.

The fabric is impregnated with the above treating agents so that the treating agents can be taken up by the fabric to an extent such that the desired fire-proof ing effect is imparted to the fabric; Usually, it is preferred that the impregnation is performed to an extent such that the treated fabric contains about-l5 to about 35 percent by weight of the treating agents as a dry weight (or solid content).

In treating the fabrics with the treating agents (1) to (5) in the method of this invention, theamounts of the treating agents (1), (2), (3), (4) and (5), when designated a, b, c, a and e respectively, must be as follows:

a 40 to 80 percent b to 50 percent 0 5 to percent d= 3 to 10 percent e= l to 5 percent In addition, these amounts should satisfy the following equation.

The range of4 to 15 in theabove formula is preferably from about 5 to about 10.

Our investigations have shown that a combination of the five treating agents, especially a combination of the treating agents (3), (4) and (5), can impart outstanding fire-proofness and moderate stiffness to fabrics composed of polyester and cellulosic filaments or fibers, and that since the total proportion of the treating agents (4) and (5) ((1% 0%) is relatively small as of the fibers is reduced to a minimum.

The fabric treated with the treating agents l to (5) is heat-set.

The heat-setting serves to form a crosslinkage among the tetrakis-hydroxymethyl phosphonium compound (1), the methylolmelamine (2) and the thioearbamic acid derivative (3) and between the cellulosic material and the organic halogenated phosphorus compound (4), promote the penetration of the treating agents into the inside of the polyester fibers, and thus to impart durability to the fabric. Preferably, the heat-setting is carried out at a temperature of about to about 200C.

In order to improve'the penetration of the organic halogenated phosphorus compound into the inside of the polyester fibers, it is desirable to pre-cure the impregnated fabric at a temperature of about 150C. for about 5 to 7 minutes,-and then heat-setting the precured fabric at a temperature of about 180 to about 200C. for about 30 seconds. This heat-setting at a later stage is also effective .for reducing the tacky feeling of the fabric by the effect of the organic halogenated phosphorus compound.

The heat-set fabric is usually soaped.

The following Examples and Comparative Examples illustrate the process of this invention in greater details. In these examples, the fire-proofness, stiffness, resistanee to dyebleed-out, rust-proofness, sticky feeling, and reistance to soiling were tested and evaluated as follows:

l. Fire-proofness 1. Test A (test in accordance with The Fire Protection Law of Japan) The fire-proofness was tested and evaluated by a testing method (45-degree microburner test) stipulated in the Fire Protection Law of Japan (Enforcement The test was carried out on the basis of Standard for the Flammability of Childrens Sleepwear (DOC FF 3-71) of US. Department of Commerce.

Five conditioned specimens, 8.9 X 25.4 cm, are suspended one at a time vertically in holders in a prescribed cabinet and subjected to a standard flame along their bottom edge for a specified time under controlled conditions. The char length and the residual flame time are measured.

An item meets the acceptance criterion if: 1) the average char length of five specimens does not exceed 17.8 cm, (2) no individual specimen has a char length of 25.4 cm and (3) no individual specimen has a residual flame time greater than 10 seconds."

(3) Test C (Match Test) This test method is being used by Southern Regional Research Laboratory, USA. [American Dyestuff Reporter, 48, p: 27 (1959)].

This test uses a strip of fabric /4 inch wide by 10 inches long, which is suspended vertically in a draftfree area and ignited at the lower end with an ordinary match. The length of flame travel is noted visually and the results are expressed by four general classifications of flame resistance: excellent if the fabric does not burn after removal of the igniting flame, good if the burning is selfextinguished in the lower 3 or 4 inches of the strip, fair" when the burning extends approximately halfway up the strip, and fail when the strip burns completely.

2. Stiffness This is determined by a 45-degree cantilever method in accordance with JIS L1079-66.

Five specimens each measuring 2 cm in warp direction and about cm in weft direction, and additional five specimens each measuring about 15 cm in warp direction and 2 cm in weft direction are prepared. Each of the specimens is placed on a horizontal stand with one end having a surface inclined at an angle of 45, and caused to slide slowly by a suitable method in the direction of the inclined surface. When the forward end makes contact with the inclined surface, the distance over which the specimen has travelled so far from the original position is measured. This distance is expressed in millimeters, and termed stiffness." The measurement is made with respect to both the surfaces and the backs of all the ten specimens, and the stiffness value is given as an average of these measured values.

3. Test for Resistance to Dye Bleed-out One piece of filter paper (Toyo Filter Paper No. l) is brought into contact with the surface and back of a specimen (dyed fabric treated by the method of this invention), 2.6 cm X 7.5 cm, and further covererd with slide glass. The assembly is fixed by a rubber ring, and then heat-treated at 80C. for 2 hours. After the heattreatment, the specimen is taken out, and the migration of the dye in the specimen to the filter paper is evaluated on the grey scale for assessing staining in color fastness in accordance with JIS L0805 (grades 1 to 5). Greater grade numbers mean lesser tendency to migration of the dye, that is, poorer resistance to dye bleedout.

Grade 5: Grade 4: Grade 3: Grade 2: Grade 1:

4. Rust-proofness An iron nail as stipulated in .118 A5508 is placed on a specimen fabric, which is then stored for 3 weeks in a desicator. Then, rust formation on the nail is observed, and evaluated on the grey scale for assessing staining in color fastness according to .115 L 0805 (grades 1 to 5). Smaller grade numbers mean greater rust formation.

Grade 5: no rust formation Grade 4: Slight rust formation Grade 3: Some rust formation Grade 2: Rust formation to an intermediate degree Grade 1: Considerable rust formation no appreciable migration slight, negligible migration some migration migration to an intermediate degree considerable migration 5. Tacky Feeling The degree of tackiness was tactually determined, and evaluated on the following scale.

Grade 1: Same as an unprocessed cloth Grade 2: Slightly greasy grade 3: Very greasy and tacky 6. Resistance to Soiling Three specimens, 5 X 5 cm, and 15 steel balls each having a diameter of 5 mm are placed in a pot, and 300 mg of an artificial soiling material consisting of 1 part by weight of carbon black, 1 part by weight of ferric oxide, 1 part by weight of ferrous oxide, 77 parts by weight of silicon dioxide, 10 parts by weight of aluminum trioxide and 10 parts by weight of magnesium oxide was added. Using a launder-O-meter, the specimens are soiled in the dry state for 30 minuteds. The soiled specimens are taken out, and placed in another pot. Water is added to the pot (at the goods-to-water ratio being 1:50), and the specimens are washed for 30 minutes. The index of reflection of the soiled specimens is measured by means of a spectrophotometer, and the rate of soiling is calculated according to the followingequation. The smaller the rate of soiling is, the better is the resistance to soiling.

Rate of staining ('7!) X wherein R is the index of reflection of the unsoiled cloth, and R, is the index of reflection of the soiled cloth.

EXAMPLES 1 TO 4 AND COMPARATlVE EXAMPLES 1 TO 3 A twill fabric (fabric weight g/m composed of polyester fibers and cotton fibers in a mixing ratio of 65:35, which had been scoured and bleached, was dipped in a dye bath of the following formulation.

Duranol Blue G (a disperse dye, a product of Imperial Chemical Industries, Ltd; Cl 63305) 2.5 g/l Mikcthrcn Blue GCD (a threnc dye. a

product of Mitsui Toatsu Chemicals Inc; Cl 69810) 5. Sodium alginatc 1 sodium hydroxide and 40 g/l of sodium sulfate,

squeezed by means of a mangle at a squeeze ratioof 80 percent, and then streamed for'l minute. The treated fabric was oxidized for 1 minute at room temperature in a treating bath containing g/l of hydrogen peroxide, finally soaped in a soaping bath containing 2 10 g/l of Marseille soap, 2 g/l of a nonionic penetrant,and I g/l of sodium carbonate at C. for 5 minutes, followed by drying at C. for 5 minutes.

The resulting dyed fabric was immersed in each of 15 the fire-proof treating baths shown in Table 1. (1n Comparative Example 1, no treatment was done.) The fabric was then squeezed by a mangle at a squeeze rate of 80 percent, dried at 120C. for 5 minutes, pre-cured at C. for 5 minutes, and heat set at C. for 30 20 '10 seconds. The fabric was then soaped in a soaping bath containing 2 g/l of Marseille soap and 2 g/l of a nonionic wetting agent at 80C. for 10 minutes, and again dried at 120C.-. for 5 minutes. The properties of the treated fabrics are shown in Table 1.

It can be seen from Table 1 that the fabrics treated in Examples 1 to 4 exhibited superior fire-proofness, and moderate stiffness, and their resistance to dye bleedout, rust-proofness, tacky feeling and soiling resistance are the same as those of the untreated cloth. On the other hand, in Comparative Example 2 in which the valueof loop/+2 a+b+c was smallerthan the lower limit specified in the present invention, the fire-proofness was insufflcient and the stiffness is inadequate. In Comparative Example 3 in which this value is larger than the upper limit specified in the present invention, the fire-proofness is insufficient, and the tacky feeling is pronounced.

Table 1 Fire-proof treat- Compara- Compara- Example 1 Example 2 Example 3 Example 4 Comparaing bath (parts tive ti ve tive by weight) Example 1 Example 2 Example 3 (1) THPC (80% aqueous (non- 25.0 25.0 25.0 25.0 1 25.0 25.0 solution) treated) (2) precondensate oftrimethylol 7.0 7.0 7.0 7.0 7.0 7.0 melamine (3) thiourea I 5.0 5.0 5.0 .5.0 i 5.0 5.0 (4) DBPP emulsion 1.5 3.5 7.0 -7.0 10.5 12.0

*1 (5) Oetadecyl ethyleneurea' 0.3 0.7 1.0 1.0 1.5 2.0 Sodium hydraxide 2.5 2.5 2.5 2.5 2.5 Water 55.7 56.3 52.5 58.8 57.1 57.9 Total 97.0 100.0 100.0 100.0 108.6 1 1 1.4

a(wt.%) 61.1 59.3 57.0 57.0 54.6 53.2 b (wt.%) 21.4 20.9 19.9 19.9 19.1 18.6 6 (wt.%) 15.3 14.8 14.2 14.2 13.6 13.3 d (w!.%) 11.4 3.1 6.0 6.0 8.6 9.6 e (11%) 0.9 2 1 2.8 2.8 41 5.3 100 (d e) b c 2.4 5.5 9.7 9.7 14.5 17.5 Take-up (wt.%) 22.2 22.5 22.7 22.4 22.0 22.0

Charred wholly 32.4 15.5 16.3 14.5 25.3 35.4 area(cm 7 burnt After Test flame time 8 0 0 0 1 5 A (sec.)

After glow 0 0 0 0 0 0 0 time (sec.) Average char Wholly 18.1 5.1 4.4 5.9 5.5 18.4 Firelength( cm) hurnt proofmaximum ness Test char 25.4 6.8 6.3 6.7 7.1 24.5

B length(cm) After flame time 1 1 0 0 0 0 7 (sec.) Test Match test C (grade) 34 2 1 1 l 1 2 Stiffness (mm) 38 58 44 40 38 38 35 Resistance to dye bleed-out (grade) 5 5 5 5 5 5 5 Rusbproofness (grade) 5 5 5 5 5 5 5 Tacky feeling (grade) 1 1 1 1 1 1 3 Resistance to soiling ("/r) 16.0 15.5 15.3 14.5 16.8 17.5 20.4

'1: An aqueous dispersion using an alkylaryl-type nonionic surfactant and an organic sulfonic acid-type anionic surfactant as an emulsifier. with a concentration of DBPP of 307: by weight.

EXAMPLE Example 2 was repeated except that trimethylolmelamine was used instead of the precondensate of trime- 12 ethyleneurea (C (Example 17), hexadecyl ethyleneurea (C (Example 18), eicosyl ethyleneurea (C (Example 19). a softening agent composed mainly of dimethyl polysiloxane (Comparative Examthylolmelamine used in Example 2. The results are 5 ple 5), and a softening agent composed mainly of polyshown in Table 2. ethylene (Comparative Example 6) were used respectively instead of the octadecyl ethyeleneneurea of Ex- EXAMPLES 6 S EEE EOMPARATWE ample 2. The results are also shown in Table 2.

It is seen that when dimethyloplysiloxane or polyeth- Example 2 was repeated except that dithiobiuret ll) ylene is used instead of the long-chain alkyl (Example 6). ethyl thiocarbamate (Example 7), cycloethyleneurea in accordance with this invention, the hexyl thiocarbamate (Example 8). propylenethiourea fabrics treated have insufficient fire-proofness and in- (Example 9), diphenylthiourea (Example 10), adequate stiffness (see Comparative Examples 5 and ethylenethiourea (Example 1 1 and urea (Comparative 6). Example 4) were used respectively instead of the thiourea in Example 2. The results are shown in Table 2. COMPARATIVE EXAMPLES 7 AND 8 It can be seen that when urea is used instead of the Example 1 was repeated except that each of the thiocarbamic acid derivatives, the fabric treated has treating baths of the following formulation indicated in poor fire-proofness and inadequate stiffness (see Com Table 3 was used. The results are shown in Table 2. The parative Example 4). treating bath of Comparative Example 7 was one described in American Dyestuff Reporter, Vol. 57, page EXAMPLES l2 TO 373, and the treating bath used in Comparative Exam- Example 2 was repeated except that a 30% emulsion ple 8 was the same bath but further containing octaof this (pentabromocresyl) phosphate (Example 12), a decyl ethyleneurea. 30% emulsion of dimethylmono(dibromocresyl) phos- 1n either case, the treated fabrics have insufficient phate (Example 13), a emulsion of his (pentafire-proofness and inadequate stiffness, and marked bromocresyl) pentabromocrcsyl phosphonate (Examdegrees of dye bleed-out, rust formation, tacky feeling ple 14). and a 30% emulsion of bis(dibromopropyl) and soiling. Incidentally, in Table 3, the value dibromopropyl phosphonate (Example 15) were used respectively instead of the DBPP emulsion of Example 30 10mm.) 2. The results are shown in Table 2. u 11+ EXAMPLES 16 TO 19 AND COMPARATIVE EXAMPLES 5 AND 6 was calculated while taking the proportion of urea as c.

Example 2 was repeated except that decyl ethyleneurea (C (Example 16). tetradecyl Table 2 Test Items Ex- Ex- Ex- Ex- Ex- Ex- Ex- Com Ex- Example ample ample ample amp ample ample paraample ample 5 s 7 s 9 10 11 tive 12 13 Exarnple 4 Charred area 14.11 18.5 18.2 19.3 17.7 24.0 18. 34.2 19 2 19.0 tern) Test After flame 0 0 0 0 0 0 0 10.0 0 0 A time (see) After glow 1 0 0 o o o a 0 0 (1 time (sec) Average char 6.0 5.1 5.0 5.7 4.8 10.5 5.1 20.5 5.7 5.0 length (cm) Fire proof- Test Maximum char 6.) 7.4 7.1 7.8 7.0 15. 7.1 25.4 7.2 7.8 ness B length (cm) After glow o 0 11 11 0 11 o 111 0 a time (see) Test 1 1 1 1 1 1 4 1 1 Stiffness (mm) 39 3'4 41 41 39 311 42 45 Resistance to dye bleed-out (grade) 5 5 5 5 5 5 5 5 5 5 Rust-proofness (grade) 5 .5 5 5 5 5 5 5 .5 5 Tacky feeling (grade) 1 l l 1 l l l l l 1 Resistance to soiling ('2) 16.8 16.5 17.2 17.0 16.) 15.4 15.7 13.3 17.3 154 Test ltems Ex- Ex- Ex Ex- Ex- Ex- Com Com- Ct1m- Comample ample ample ample ample ample para paraparapara l4 l5 l6 l7 18 19 live live tive tive Ex Ex- Ex- Example ample ample ample s 6 7 s Charred area 19.0 19.3 23.9 21 20.11 17.8 311.5 40.2 22.0 21.5 (cm) Test After flame 0 0 0 0 0 0 2 1 2X 5 5 A time (see) After m 0 u u 11 11 o 1 3 (1 11 time (sec) Average char 5.1 5.0 10.2 11.8 7.0 5 6 II 4 33.4 13. 14.1

Table Z-continued Test ltems Ex- Ex- Ex- Ex- Ex- E Y.\'- Con Ex Example ample ample ample ample ample ample paraample ample 6 7 l1 9 10 l 1 five 12 1.

Example 4 length (cm) Fire Proof Test Maximum char 9.0 7.0 15.0 12.2 10.1 7.5 25.4 25.4 25.4 25.4 ncss B length (cm) After glow 0 0. 0 0 0 0 12 15 7 10 time (sec) Test 1 1 1 1 1 1 4 4 1 3 C Stiffness (mm) 39 42 54 49 45 42 72 70 22 Resistance to dye bleed-out 5 5 5 5 5 5 5 5 l I (grade) Rust-proofncss (grade) 5 5 5 5 5 5 5 5 2 2 Tacky feeling (grade) 1 l l l l I l l 3 3 Resistance to soiling (71) 18.1 17.4 15.4 16.3 14.6 14.3 17.1 19.0 30.5 31.7

* In a comparison in which urea was used instead of the thiocarbamic acid derivative of this invention 100(d+u) the weight percent of urea as c. was calculated mkmg Table 3 Treating bath Comparative Comparative Example 7 Example 8 THPC (80% aqueous solution) 25.0 25.0 Precondensate of trimethylol melamine 7.0 7.0 Urea 5.0 5.0 DEPP emulsion *1 43.0 43.0 Octadecyl ethyleneurea 4 1.0 Sodimum hydroxide 2.5 2.5 Water 17.5 16.5 Total 100.0 100.0

100 (d e) +b+ C 40.3 43.5 Take-up (weight '70) 27.5 24.1

1: See the footnote to Table 1 EXAMPLE 20 The same twill fabric as used in Example 1 was dipped in a treating bath containing 1.8 parts of tris (2,3-dibromopropy1) phosphate and 98.2 parts of toluene, squeezed by a mangle at a squeeze ratio of 75 percent, and then dried at 120C. for 5 minutes. The take-up of the organic halogenated phosphorus compound was 1.35 percent. The treated fabric was further immersed in a treating bath consisting of 25.0 parts of Tl-[PC (80% aqueous solution), 7.0 parts of a precondensate of trimethylolmelamine, 5.0 parts of thiourea, 1.0 part of octadecylethyleneurea, 2.5 parts of sodium hydroxide, and 59.5 parts of water, squeezed at by a mangle at a squeeze ratio of 80 percent, dried at 120C. for 5 minutes, and cured at 150C. for 5 minutes.

The amount of the treating agent newly adhered was 21.2 percent. The treated fabric was further heat-set at 180C. for seconds. Then, the fabric was soaped in a soaping solution consisting of 2 g/l of Marseille soap and 2 g/l of a nonionic wetting agent at 80C. for 10 minutes, and dried at 120C. for 5 minutes. The proportions u, b, c, d and e of the treating agents, and the value and the other results obtained are shown in Table The fabrics treated in accordance with the method of this invention have superior fire-proofness and other various properties.

Table 4 items Examples 20 a 56.9 b 200 c 14.2 d 6.0 c 2.8 100 (d e) w 9.7 a h c Fire-proofness 112,1/5 Test A Charred area (cm 15.8 After flame time (seconds) 0 After glow time (seconds 0 Test B Average char length (cm) 40 Maximum char length (cm) 5.8

After flame time (seconds) 0 Bi l Stiffness (mm) 38.2 Resistance to dye bleedl-out (grade) 5 Rust-proofness (grade) 5 Tackiness (grade) 1 Resistance to soiling (7:) 13.7

What is cla1med 1s:

1. A method for fire-proofing treatment of a fabric composed of polyester and cellulosic filaments of fabers, which comprises impregnating said fabric with the following treating agents (1) to (5) l. a tetrakis-hydroxymethyl phosphonium compound, 2. methylolmelamine, 3. a thiocarbamic acid derivative expressed by the following formula the amounts of the treating agents (1), (2), (3), (4) and 5 (5), when designated a, b, c, d and 2 respectively, being as follows based on the total weight of a to e wherein X is a group selected from the class consisting of and OR;,, each ofR R R R, and R is a hydrogen atom or a hydrocarbon group containing 1 to 12 carbon atoms, and R or R may, together with X, form a cyclic structure,

4. an organic halogenated phosphorus compound selected from the group consisting of wherein R R and R,, are the same or different, and each represent a monovalent hydrocarbon group containing 1 to 12 carbon atoms, at least one of R R and R contains at least one halogen atom selected from the group consisting of bromine and chlorine, R R and R are the same or different and each represent a monovalent hydrocarbon group containing 1 to 12 carbon atoms, and at least wherein R is a monovalent saturated alkyl group containing 8 to 22 carbon atoms,

a to 80 percent b 10 to percent 6 5 to 25 percent a 3 to 10 percent e l to 5 percent and satisfying the following equation contains said treating agents in an amount of about 15 to about 35 percent as dry weight based on the weight of the fabric.

3. The method of claim 1 wherein the heat-setting is carried out at a temperature of about l50 to about 200Cv 4. The method of claim 1 wherein said fabric consists of about 50 to about percent by weight of the polyester filaments or fibers and about 50 to about 30 percent by weight of the cellulosic filaments or fibers, both based on the weight of the fabric.

5. The method of claim 1 wherein said tetrakishydroxymethyl phosphonium compound (l) is a compound selected from the group consisting of tetrakishydroxymethyl phosphonium chloride and tetrakishydroxymethyl phosphonium hydroxide, said thiocarbamic acid derivative (3) is a compound expressed by the following formula wherein each of R and R' is a hydrogen atom or a hydrocarbon group containing 1 to 6 carbon atoms, and R or R may, together with NH form a cyclic structure having a lower alkylene linkage,

said organic halogenated phosphorus compound is a compound selected from the group consisting of organic halogenated phosphorus compounds of the forwherein R,;, R and R are the same or different and each represent a monovalent hydrocarbon group containing 1 to 6 carbon atoms, preferably an alkyl group containing 1 to 6 carbon atoms or a phenyl group that may be substituted by a lower alkyl group containing 1 to 4 carbon atoms, at least one of R' R and R',; contains at least one halogen atom selected from the group consisting of bromine and chlorine, R,,, R', and R are the same or different, and each represent a monovalent hydrocarbon group containing 1 to 6 carbon atoms, preferably an alkyl group containing 1 to 6 carbon atoms or a phenyl group that may be substituted with a lower alkyl group containing 1 to 4 carbon atoms, and at least one of R' R and R con tains at least one halogen atom selected from the group consisting of bromine and chlorine, and said long-chain alkyl ethyleneurea (5) is a compound expressed by the following formula octadecyl ethylencurea. v 

1. AMETHOD FOR FIRE-PROOFING TREATMENT OF A FABRIC COMPOSED OF POLYESTER AND CELLULOSIC FILAMENTS OF FABERS, WHICH COMPRISES IMPREGNATING SAID FABRIC WITH THE FOLLOWING TREATING AGENTS (1) TO (5)
 1. A TETRAKIS-HYDROXYMETHYL PHOSPHONIUM COMPOUND,
 2. METHYLOLMELAMINE,
 2. methylolmelamine,
 2. The method of claim 1 wherein said treated fabric contains said treating agents in an amount of about 15 to about 35 percent as dry weight based on the weight of the fabric.
 3. The method of claim 1 wherein the heat-setting is carried out at a temperature of about 150* to about 200*C.
 3. a thiocarbamic acid derivative expressed by the following formula
 3. A THIOCARBAMIC ACID DERIVATIVE EXPRESSED BY THE FOLLOWING FORMULA
 4. AN ORGANIC HALOGENATED PHOSPHORUS COMPOUND SELECTED FROM THE GROUP CONSISTING OF
 4. an organic halogenated phosphorus compound selected from the group consisting of
 4. The method of claim 1 wherein said fabric consists of about 50 to about 70 percent by weight of the polyester filaments or fibers and about 50 to about 30 percent by weight of the cellulosic filaments or fibers, both based on the weight of the fabric.
 5. The method of claim 1 wherein said tetrakishydroxymethyl phosphonium compound (1) is a compound selected from the group consisting of tetrakis-hydroxymethyl phosphonium chloride and tetrakis-hydroxymethyl phosphonium hydroxide, said thiocarbamic acid derivative (3) is a compound expressed by the following formula
 5. a long-chain alkylethyleneurea of the formula
 5. A LONG-CHAIN ALKYLETHYLENEUREA OF THE FORMULA
 6. The method of claim 5 wherein said thiocarbamic acid derivative (3) is thiourea, said organic halogenated phosphorus compound (4) is a compound selected from the group consisting of tris(2,3-dibromopropyl) phosphate, tris(bromochloropropyl) phosphate and bis(dibromopropyl) dibromopropyl phosphonate, and said long-chain alkyl ethyleneurea (5) is octadecyl ethyleneurea. 